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Fabrication and performance of asymmetric tubular H 2 membranes - - PowerPoint PPT Presentation

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1 Fabrication and performance of asymmetric tubular H 2 membranes based on LWM-LSC composites Zuoan Li, Marie-Laure Fontaine, Jonathan M. Polfus, Christelle Denonville, Wen Xing, Partow P. Henriksen, Rune Bredesen SINTEF Materials and

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SLIDE 1

Fabrication and performance of asymmetric tubular H2 membranes based on LWM-LSC composites

Zuoan Li, Marie-Laure Fontaine, Jonathan M. Polfus, Christelle Denonville, Wen Xing, Partow P. Henriksen, Rune Bredesen

SINTEF Materials and Chemistry, Sustainable Energy Technology, Oslo, Norway

1

This publication has been produced with support from the BIGCCS Centre, performed under the Norwegian research program Centres for Environment-friendly Energy Research (FME). The authors acknowledge the following partners for their contributions: Gassco, Shell, Statoil, TOTAL, ENGIE, and the Research Council of Norway (193816/S60).

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SLIDE 2

2

  • Hydrogen permeation in asymmetric membranes
  • Fabrication of LWM-LSC tubular membranes
  • Hydrogen flux of LWM-LSC tubes
  • Numerical simulation of gas transport
  • Stability of membranes
  • Summary

Outline

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SLIDE 3

Dense ceramic H2 membranes

►Power production

  • Pre-combustion CCS

►Chemicals production

  • H2 purification
  • Catalytic membrane reactors
  • Hydrogenation
  • Dehydrogenation

3

Main challenges 1.Fabrication and cost 2.Low flux 3.Membrane stability

  • Novel thin film supported cercer

membranes

  • Study of transport mechanisms
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SLIDE 4

Hydrogen permeation

4

Ar

Porous support Dense membrane

Inlet

H2 + He + H2O H2 + Ar

Outlet Outlet

Depleted H2 + He + H2O H+

Sweep Inlet

e-

I 2

H

II 2

H

III 2

H

Dry sweep + Wet feed

Feed

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SLIDE 5

Hydrogen permeation

5

Ar + H2O

Inlet

H2 + He + H2O H2 + Ar + H2O

Outlet Outlet

Depleted H2 + He + H2O H+

Sweep Feed Inlet

e- O2-

I 2

H

I 2

O

II 2

H

II 2

O

II 2

H O

III 2

H O

III 2

H + = +

I 2

H

I 2

H O

Wet sweep + Wet feed

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SLIDE 6

►La27W3.5Mo1.5O55-d (LWM)

  • High proton conductivity
  • Chemical stability

►La0.87Sr0.13O3-d (LSC)

  • High p-type conductivity
  • High oxide ion conductivity

Cercer membrane materials

6

2) A. Magraso, R. Haugsrud, J. Mater. Chem. 2 (2014) 12630. 1) J.M. Polfus, et al., J. Mem. Sci. 479 (2015) 39. 3) Y. Larring, et al., Membranes 2 (2012) 665. LWM (70%)-LSC (30%) LWM

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SLIDE 7

Fabrication of asymmetric membranes

7

Powder conditioning, suspension and dough preparation Extrusion and drying of LWM tubes in clean room class 7 Cutting and bisque firing of LWM tubes at 1300 oC: 20-30 cm pieces; hang-firing Dip-coating of bisque fired tubes in clean room class 7 : LWM-LSC suspension Sintering of membranes at 1500 oC: Hang-firing, in air

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SLIDE 8

935 940 945 950 955 960 965 970 1.0E-14 1.5E-14 2.0E-14 2.5E-14 3.0E-14

LWM supports

Permeability (m

2)

P_high (mbar)

Sintered porous supports and membranes

8

Permeability of LWM supports Leak test at RT of asymmetric membranes

0.0 0.5 1.0 1.5 2.0 2.5 3.0 5E-7 5E-6 5E-5 5E-4 0.005

p (bar) Gas leakage (mL / cm

2 min)

Helium Oxygen

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SLIDE 9

Testing protocols

9

Hydrogen flux testing setup

 Sealing: glass-ceramic  1000-1100 °C  Tube outer surface:  No coating/Pt coated  Feed: Wet H2  Sweep: Dry/wet Ar  2.5% H2O  Temperature: 1100-750 °C

Testing conditions

Retentate ZrO2 cap GC ZrO2 support Feed Wet H2 Sweep Ar or Wet Ar LWM/LSC membrane

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SLIDE 10

Hydrogen flux

Higher flux when using wet sweep and Pt coating

0.70 0.75 0.80 0.85 0.90 0.95 1.00 1.05 1E-3 0.01 Sweep: 25 mL/min Ar Feed: 25 mL/min H2+25 mL/min He (wet)

J (H2) (mL/min cm

2)

Wet sweep (Pt coated tube) Dry sweep (Pt coated tube) Wet sweep (uncoated tube) Dry sweep (uncoated tube)

1000/T (K

  • 1)

1100 1000 900 800 700

T (°C)

10

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SLIDE 11

Hydrogen permeability

11

  • Dry sweep:

comparable between tubular and disc membranes

  • Wet sweep:

much higher flux for disc than thinner tubular membrane !! Why water splitting is so different between disc and tube?

LWM (70%) - LSC (30%)

80 microns versus 1 mm thick membranes

0.7 0.8 0.9 1.0 1.1 1E-5 1E-4 1E-3

Sweep: 25 mL/min Ar Feed: 25 mL/min H2 + 25 mL/min He (wet)

Permeability (H2) (mL/min/cm)

Dry - Pt coated tube - this work Dry - Pt coated disc - Polfus et al. Wet - Pt coated tube - this work Wet - Pt coated disc - Polfus et al.

1000/T (K

  • 1)

1100 1000 900 800 700 600

°C

LWM LWM (70%) - LSC (30%)

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SLIDE 12

Exchange feed and sweep sides

12

Porous support is not limiting!

0.84 0.86 0.88 0.90 0.92 0.94 0.01 0.015 0.02 0.025 0.03

Sweep: 25 mL/min Ar Feed: 25 mL/min H2+25 mL/min He (wet)

J (H2) (mL/min/cm

2)

Wet outer sweep Wet inner sweep Dry outer sweep Dry inner sweep

1000/T (K

  • 1)

900 880 860 840 820 800

°C

Sweep Feed Feed Sweep

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SLIDE 13

Numerical simulations of gas transport

13

O2, H2, H2O, Ar Porous Media

LWM/LSC membrane layer

H2O splitting

LWM support

         

g ,Kn ,Kn

J J J

l k k l k k k e e e l k T kl k k

B X X X X p X D D D 

     

g e kl kl

D D   

p ,Kn

4 8 3

g e k k

r RT D W    

Implementation

Solve steady state flux!

I 2 2 2 II 2 2

pO H O H 2 2 O e pO

d(lnpO ) 8 RT J t F L 

 

 

II 2 I 2 2

pH Perm H 2 2 H e pH

d(lnpH ) 4 RT J t F L 

 

 

H2 permeation

Finite volume, Matlab & Cantera

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SLIDE 14

Calculated pH2 gradient under WF+DS

14

0.0 0.2 0.4 0.6 0.8 1.0 1.2 0.01 0.1 Dry sweep Sweep

pH2

Feed T = 900 °C

pH2 (atm) r (mm)

LWM support

LWM-LSC 50 m

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SLIDE 15

Numerical simulations under WF+WS

15 0.0 0.2 0.4 0.6 0.8 1.0 1.2 0.01 0.1 Wet sweep Sweep Interface

pH2 pH2O

Feed T = 900 °C

pH2 & pH2O (atm) r (mm)

0.0 0.2 0.4 0.6 0.8 1.0 1.2 1E-19 1E-18 1E-17 1E-16 Feed

pO2

pO2 (atm) r (mm)

Wet sweep T = 900 °C Sweep

Oxygen surface kinetics at the interface!!!

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SLIDE 16

16

40 m

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SLIDE 17

Stability of tubular LMW/LSC membrane

17

0.80 0.85 0.90 0.95 1.00 0.000 0.005 0.010 0.015 0.020 Sweep side: 25 mL/min Ar (wet) Feed side: 25 mL/min H2+25 mL/min He (wet)

J (H2) (mL/min cm

2)

Cooling from 1000 to 850 °C Heating from 850 to 1000 °C Heating from 850 to 950 °C (1 week later) Cooling from 950 to 750 °C (1.5 week later)

1000/T (K

  • 1)

1000 950 900 850 800 750

T (°C)

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SLIDE 18

Stability of Pt coated LMW/LSC tube

18

0.70 0.75 0.80 0.85 0.90 0.95 1.00 1.05 1E-3 0.01

Sweep: 25 mL/min Ar Feed: 25 mL/min H2+25 mL/min He (Wet)

J (H2) (mL/min cm

2) Wet sweep (cooling:1100-700°C, 1st) Wet sweep (heating:700-1000°C, 2nd) Dry sweep (cooling:1000-700°C, 3rd) Dry sweep (heating:700-1000°C, 4th) Wet sweep (cooling:1000-950°C, 5th - 10 days later) Wet sweep (cooling:900-850°C, 6th - 18 days later) Dry sweep (cooling:850-800°C, 7th - 20 days later) Wet sweep (cooling:800-750°C, 8th - 26 days later)

1000/T (K

  • 1)

1100 1000 900 800 700

T (°C)

100 200 300 400 5.0E-3 1.0E-2 T = 750 °C Sweep: 25 mL/min Ar (wet) Feed: 25 mL/min H2 + 25 mL/min He (wet)

J (H2) (mL/min/cm

2)

Time (h)

One month Anthoer 17 days

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SLIDE 19

Summary

19

►Fabrication of tubular LWM/LSC cercer membrane on LWM support with scaleable process was achieved ►Interface between the membrane and the support is critical, especially for water splitting or oxygen incorporation. ►Membranes (Pt coated and uncoated) are stable.